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Linking soil architecture formation with changing permafrost regime to carbon turnover in high latitude soils at multiple spatial scales

Most soils develop distinct soil architecture during pedogenesis and soil organic carbon (SOC) is sequestered within a hierarchical system of mineral-organic associations and aggregates. Permafrost soils store large amounts of carbon due to their permanently frozen subsoil and a lack of oxygen in the active layer, but they lack complex soil structure. With permafrost thaw more oxidative conditions and increasing soil temperature presumably enhance the build-up of more complex units of soil architecture and may counterbalance, at least partly, SOC mineralization. We aim to explore the development of mineral-organic associations and aggregates under different permafrost impact with respect to SOC stabilization. This information will be linked to environmental control factors relevant for SOC turnover at the pedon and stand scale to bridge processes occurring at the aggregate scale to larger spatial dimensions. We will combine in situ spectroscopic techniques with fractionation approaches and identify mechanisms relevant for SOC turnover at different scales by multivariate statistics and variogram analyses. From this we expect a deeper knowledge about soil architecture formation in the transition of permafrost soils to terrestrial soils and a scale-spanning mechanistic understanding of SOC cycling in permafrost regions.

Release of hexavalent chromium from ore processing residues and the potential of biochar for chromium immobilization in polluted soils

Chromium (Cr) is introduced into the environment by several anthropogenic activities. A striking ex-ample is the area around Kanpur in the Indian state of Uttar Pradesh, where large amounts of Cr-containing wastes have been recently illegally deposited. Hexavalent Cr, a highly toxic and mobile contaminant, is present in significant amounts in these wastes, severely affecting the quality of sur-roundings soils, sediments, and ground waters. The first major goal of this study is to clarify the solid phase speciation of Cr in these wastes and to examine its leaching behavior. X-ray diffraction and synchrotron-based X-ray absorption spectroscopy techniques will be employed for quantitative solid phase speciation of Cr. Its leaching behavior will be studied in column experiments performed at un-saturated moisture conditions with flow interruptions simulating monsoon rain events. Combined with geochemical modeling, the results will allow the evaluation of the leaching potential and release kinetics of Cr from the waste materials. The second major goal is to investigate the spatial distribution, speciation, and solubility of Cr in the rooting zone of chromate-contaminated soils surrounding the landfills, and to study the suitability of biochar as novel soil amendment for mitigating the deleterious effects of chromate pollution. Detailed field samplings and laboratory soil incubation studies will be carried out with two agricultural soils and biochar from the Kanpur region.

Ecotoxicology of Organotin compounds

Organotin and especially butyltin compounds are used for a variety of applications, e.g. as biocides, stabilizers, catalysts and intermediates in chemical syntheses. Tributyltin (TBT) compounds exhibit the greatest toxicity of all organotins and have even been characterized as one of the most toxic groups of xenobiotics ever produced and deliberately introduced into the environment. TBT is not only used as an active biocidal compound in antifouling paints, which are designed to prevent marine and freshwater biota from settlement on ship hulls, harbour and offshore installations, but also as a biocide in wood preservatives, textiles, dispersion paints and agricultural pesticides. Additionally, it occurs as a by-product of mono- (MBT) and dibutyltin (DBT) compounds, which are used as UV stabilizer in many plastics and for other applications. Triphenyltin (TPT) compounds are also used as the active biocide in antifouling paints outside Europe and furthermore as an agricultural fungicide since the early 1960s to combat a range of fungal diseases in various crops, particularly potato blight, leaf spot and powdery mildew on sugar beet, peanuts and celery, other fungi on hop, brown rust on beans, grey moulds on onions, rice blast and coffee leaf rust. Although the use of TBT and TPT was regulated in many countries world-wide from restrictions for certain applications to a total ban, these compounds are still present in the environment. In the early 1970s the impact of TBT on nontarget organisms became apparent. Among the broad variety of malformations caused by TBT in aquatic animals, molluscs have been found to be an extremely sensitive group of invertebrates and no other pathological condition produced by TBT at relative low concentrations rivals that of the imposex phenomenon in prosobranch gastropods speaking in terms of sensitivity. TBT induces imposex in marine prosobranchs at concentrations as low as 0,5 ng TBT-Sn/L. Since 1993, for the littorinid snail Littorina littorea a second virilisation phenomenon, termed intersex, is known. In female specimens affected by intersex the pallial oviduct is transformed of towards a male morphology with a final supplanting of female organs by the corresponding male formations. Imposex and intersex are morphological alterations caused by a chronic exposure to ultra-trace concentrations of TBT. A biological effect monitoring offers the possibility to determine the degree of contamination with organotin compounds in the aquatic environment and especially in coastal waters without using any expensive analytical methods. Furthermore, the biological effect monitoring allows an assessment of the existing TBT pollution on the basis of biological effects. Such results are normally more relevant for the ecosystem than pure analytical data. usw.

Root distribution and dynamics and their contribution to subsoil C-fluxes

It has been suggested that dying and decaying fine roots and root exudation represent important, if not the most important, sources of soil organic carbon (SOC) in forest soils. This may be especially true for deep-reaching roots in the subsoil, but precise data to prove this assumption are lacking. This subproject (1) examines the distribution and abundance of fine roots (greater than 2 mm diameter) and coarse roots (greater than 2 mm) in the subsoil to 240 cm depth of the three subsoil observatories in a mature European beech (Fagus sylvatica) stand, (2) quantifies the turnover of beech fine roots by direct observation (mini-rhizotron approach), (3) measures the decomposition of dead fine root mass in different soil depths, and (4) quantifies root exudation and the N-uptake potential with novel techniques under in situ conditions with the aim (i) to quantify the C flux to the SOC pool upon root death in the subsoil, (ii) to obtain a quantitative estimate of root exudation in the subsoil, and (iii) to assess the uptake activity of fine roots in the subsoil as compared to roots in the topsoil. Key methods applied are (a) the microscopic distinction between live and dead fine root mass, (b) the estimation of fine and coarse root age by the 14C bomb approach and annual ring counting in roots, (c) the direct observation of the formation and disappearance of fine roots in rhizotron tubes by sequential root imaging (CI-600 system, CID) and the calculation of root turnover, (d) the measurement of root litter decomposition using litter bags under field and controlled laboratory conditions, (e) the estimation of root N-uptake capacity by exposing intact fine roots to 15NH4+ and 15NO3- solutions, and (f) the measurement of root exudation by exposing intact fine root branches to trap solutions in cuvettes in the field and analysing for carbohydrates and amino acids by HPLC and Py-FIMS (cooperation with Prof. A. Fischer, University of Trier). The obtained data will be analysed for differences in root abundance and activity between subsoil (100-200 cm) and topsoil (0-20 cm) and will be related to soil chemical and soil biological data collected by the partner projects that may control root turnover and exudation in the subsoil. In a supplementary study, fine root biomass distribution and root turnover will also be studied at the four additional beech sites for examining root-borne C fluxes in the subsoil of beech forests under contrasting soil conditions of different geological substrates (Triassic limestone and sandstone, Quaternary sand and loess deposits).

Diffusion and advection with sorption of anions, cations and non-polar molecules in organo-clays at varying thermo-chemical conditions - validation by analytical methods and molecular simulation

The sorption of anions in geotechnical multibarrier systems of planned high level waste repositories (HLWR) and of non-ionic and organic pollutants in conventional waste disposals are in the center of recent research. In aquatic systems, persistent radionuclides such as 79Se, 99Tc, 129I exist in a form of anions. There is strongly increasing need to find materials with high sorption capacities for such pollutants. Specific requirements on barrier materials are long-term stability of adsorbent under various conditions such as T > 100 C, varying hydrostatic pressure, and the presence of competing ions. Organo-clays are capable to sorb high amounts of cations, anions and non-polar molecules simultaneously having selectivity for certain ions. This project is proposed to improve the understanding of sorption and desorption processes in organo-clays. Additionally, the modification of material properties under varying chemical and thermal conditions will be determined by performing diffusion and advection experiments. Changes by sorption and diffusion will be analyzed by determining surface charge and contact angles. Molecular simulations on models of organo-clays will be conducted in an accord with experiments with aim to understand and analyze experimental results. The computational part of the project will profit from the collaboration of German partner with the group in Vienna, which has a long standing experience in a modeling of clay minerals.

Physicochemical Aging Mechanisms in Soil Organic Matter (SOM- AGING): II. Hydration-dehydration mechanisms at Biogeochemical Interfaces

Soil organic matter (SOM) controls large part of the processes occurring at biogeochemical interfaces in soil and may contribute to sequestration of organic chemicals. Our central hypothesis is that sequestration of organic chemicals is driven by physicochemical SOM matrix aging. The underlying processes are the formation and disruption of intermolecular bridges of water molecules (WAMB) and of multivalent cations (CAB) between individual SOM segments or between SOM and minerals in close interaction with hydration and dehydration mechanisms. Understanding the role of these mediated interactions will shed new light on the processes controlling functioning and dynamics of biogeochemical interfaces (BGI). We will assess mobility of SOM structural elements and sorbed organic chemicals via advanced solid state NMR techniques and desorption kinetics and combine these with 1H-NMR-Relaxometry and advanced methods of thermal analysis including DSC, TGADSC- MS and AFM-nanothermal analysis. Via controlled heating/cooling cycles, moistening/drying cycles and targeted modification of SOM, reconstruction of our model hypotheses by computational chemistry (collaboration Gerzabek) and participation at two larger joint experiments within the SPP, we will establish the relation between SOM sequestration potential, SOM structural characteristics, hydration-dehydration mechanisms, biological activity and biogechemical functioning. This will link processes operative on the molecular scale to phenomena on higher scales.

Nachbewilligung zur Dritten Phase des Projektes: Entwicklung eines zweistufigen biologischen Verfahrens zur Reinigung von Deponiesickerwasser und industriellen Abwässern mit komplexen Stoffgemischen

Zielsetzung und Anlass des Vorhabens: Ziel der letzten Projektphase war es, mit einer Langzeit-Praxiserprobung das zweistufige biologische Verfahren zur Deponiesickerwasserreinigung als Stand der Technik zu etablieren und zu bilanzieren. Nach der Inbetriebnahme des Technikums am Deponiestandort Schöneiche ging es in der zwölfmonatigen Laufzeit des Projektes AZ 14996/04 in den Langzeitversuchen um die Validierung der Laborergebnisse im technischen Maßstab, die verfahrenstechnische Optimierung der Anlage und um eine damit verbundene mögliche Kostenreduzierung des Systems. Darstellung der Arbeitsschritte und der angewandten Methoden: Nach dem ersten Technikums-Probebetrieb wurde eine Reihe von Optimierungsmaßnahmen durchgeführt: - der Umbau des Rohsickerwasserzulaufs, - die Verwendung von Soda statt Bicarbonat für die Ammoniumoxidation in Reaktor 2, - der Einsatz von Membrandosierpumpen mit integrierten Rückschlagventilen für die Zugabe von Soda und Essigsäure, - der Einbau von zusätzlichen Polyurethan-Festbetten zur Vergrößerung der Oberfläche für die Besiedlung mit Mikroorganismen, - die Einstellung des Sollwerts für Reaktor 4 auf einen pH-Wert von 6,5, - ein Update der SPS-Steuerung der Nanofiltration zur freien Programmierung der Spülzyklen, - der Einbau eines Absperrhahns vor den Nanofiltrations-Vorfilter - und die Trennung des Nanofiltrationsablaufs vom Reaktoren-Sammelablauf zur Behälterleerung. Es wurde sowohl Rohsickerwasser der MEAB-Deponie Schöneiche als auch Sickerwasserkonzentrat der Deponie Vorketzin behandelt. Fazit: Wegen der durchgeführten Optimierungsmaßnahmen ist es prinzipiell gelungen, das Schöneicher Rohsickerwasser gemäß Anhang 51 der Abwasserverordnung aufzureinigen. In Vorketzin wurde die organische Belastung über 70% und Stickstoff über 80% reduziert. Nach Rückgang der Calciumfracht sollte es zukünftig möglich sein, mit der Zweistufen-Biologie das Sickerwasserkonzentrat ausreichend zu reinigen, da organische Belastung und Stickstoffgehalt geringer als im Schöneicher Rohsickerwasser sind. Um das Verfahren als Stand der Technik, vor allem für die Behandlung von Sickerwasserkonzentraten, zu etablieren, müssten die Laborvorgaben mit den Erfahrungen des Technikumsbetriebs kombiniert und in einer weiteren Versuchsreihe unter optimierten Bedingungen verifiziert werden.

The scalar organization of environmental governance: an institutionalist perspective on the transformation of water and marine governance in the European Union

The project aims to theorize the scalar organization of natural resource governance in the European Union. This research agenda is inspired by critical geographers' work on the politics of scale. The research will examine an analytical framework derived from theories of institutional change and multi-level govern-ance to fill this theoretical gap. Furthermore, it will review conceptualizations of the state in institutional economics, evaluate their adequacy to capture the role of the state in the dynamics identified, and develop them further. The described processes may imply shifts in administrative levels, shifts in relations between different levels and changes in spatial delimitations of competent jurisdictions that result, for example, from decentralization or the introduction of river basin oriented administrative structures. The research investigates the implications of two European Directives: the Water Framework Directive (WFD) and the Marine Strategy Framework Directive (MSFD). They both have potentially great significance for the organization of marine and water governance at the level of Member States and below, and adhere to similar regulatory ideas for achieving good ecological status of waters. A multiple case study on changes in the scalar reorganization of marine and water governance that result from the implementation of the Directives will be carried out. It will rely on qualitative and quantitative data gathering based on semi-structured interviews and review of secondary and tertiary sources looking at Portugal, Spain, and Germany. It specifically addresses the role of social ecological transactions, the structure of decision making processes and the role of changes in contextual factors (such as ideologies, interdependent institutions and technology).

Beach sand deposits on the coast of southern Norway as a natural experimental setup to test hypotheses on soil development and luminescence dating

Beach sand deposits are widespread in the area around Sandefjord, at the western coast of the Oslofjord, southern Norway. The age of the deposits continuously increases with elevation, as the area has been subject to steady glacio-isostatic uplift throughout the Holocene. Existing local sea level curves provide age control related to elevation. Thus, the area offers excellent conditions to test hypotheses on soil formation and OSL dating. A chronosequence covering the last 10 000 years will be established. A preliminary study showed that soil formation leads to Podzols within 4300 - 6600 years. Micromorphological analyses suggest that clay illuviation takes place before and below podzolisation. It is hypothesised that clay translocation goes on contemporarily with podzolisation, but at greater soil depth, where the chemical conditions are suitable. This hypothesis will be proved by more detailed micromorphological investigation and chemical analyses. The factors controlling soil forming processes and their rates, will be determined by analyzing elemental composition, primary minerals and clay mineralogy. Preliminary OSL dating tests suggest that the beach sand deposits are OSL dateable despite the high latitude. This hypothesis will be checked by comparing OSL datings to ages derived from the 14C-based sea level curves.

Impact of urbanisation on the allergenicity of birch pollen grains

Evidence is compelling for a positive correlation between urbanisation and increment of allergic sensitisation and diseases. The reason for this association is not clear to date. Some data point to a pro-allergic effect of anthropogenic factors on susceptible individuals. Data analysing the impact of environmental - natural and anthropogenic - factors on the allergenicity of allergen carriers such as pollen grains are scarce, and if applicable only taken from in vitro experimental designs. This study will analyse one of the most common allergy inducers in northern Europe - the birch pollen. Under natural exposure conditions, birch pollen will be analysed with respect to their allergenicity. Within an interdisciplinary research team this study will evaluate the effect of natural (e.g. soil, climate, genetic background) and anthropogenic (e.g. traffic pollutants) factors on birch pollen in a holistic approach including analysis of allergen bioavailability, release of pollen associated lipid mediators from birch pollen grains, in vitro immunostimulatory activity and in vivo allergenic potential. These data collected in the time course of three years will significantly add to our understanding how urbanisation and climate change influence the allergenicity of birch pollen and will help us in the future to set up primary prevention studies.

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